Azo arylides of 2.3 hydroxy-naphthoic acid and azo dyestuffs derived therefrom



Patented Sept. 13, 1932 COMPANY, or MIDLAND, MICHIGAN, A CORPORATION oF IoHIeAN AZO ARYLILDES OF 2.3 HYDROXY-NAPHTI-IOIG ACID AND V 'IHEREFROM No Drawing. Application filed April 27,

The invention relates to direct developed azo dyestuffs of thetype'wherein an arylide of 2.3 hydroxy naphthoic acid is coupled with a diazotized arylamine, and has regard par- 5 ticularly to a new sub-class of the above general character but distinguished from those hitherto known in that the aforesaid arylide: component thereof is formed by condensing an'amino-azo compound, instead of a simple 1 arylamine, with 2.3-hydro-naphthoic acid.

That is to say, the dyestuffs of the present invention are to be denoted as the coupled product of diazotized or tetrazotized arylamines and azo-arylides of 2.3-hydro-naphthoic acid.

. They accordingly have the structure of disazo or polyazo compounds, which is illustrated 'by the following general formula, representing such disazo compound in which R, Rf and X, respectively, are aryl residues which maybe further substituted.

It is: well known that direct azo dyes fast to light and Washing are produced by coupling arylides of QB-hydr Xy-naphthOic acid with diazotized ortetrazotized. arylamines, as is evidenced by the large number of. issued patents bearing on the subject. I have discovered, however, that, when azo-arylides of 2.3-hydroXy-naphthoic' acid are so coupled, the dyestuffs produced possess even greater fastness and the colors developed are notably deeper in tone. The invention, then, consists of the new intermediate compounds, viz., azoarylides of 2.3-hydroXy-naphthoic acid, and azo dyestuffs derived therefrom, together with the methods for the preparation thereof as hereinafter fully described and particular ly pointed out in the claims, the following representative of various ways in which the principle of the invention may bepracticed. The herein described new dyestuffs dye cotton and other fibres directly in a wide range 7 of colors varying from orange to deep blue from meta-nitraniline is a clear, deeporange. ;The has the description setting forth certain procedure I l 1929. Serial No. 358,756.

and black and in remarkably clear and brilliant tones, They are best applied bydeveloping on the fibre, but may also beproduced in substance per se or deposited upon' suitable substrata to'form lakes, in which forms they are useful pigments on account of their insolubility, stability and fastness.

A preferred manner in which the invention may be carried out is illustrated in the following specific examples, it being understood,

however, that such examples are not to be construed as-a limitation uponthe invention.

Examplel The benzene azo arylide of QB-hydro y naphthoic acid is prepared by heating a mix- PATENT Q FL E ERNEST r. GRETHER, or MIDLAND, MICHIGAN,

ASSIGNOR TO .THE' now CHEMICAL :IAZO nrns'rnrrs DERIVED ture consisting of 20 parts aminol-azo-benzene,

2J0 parts 2.3-hydroxy-naphthoicj acid and 6 7 parts phosphorus trichloride' dissolved or suspended in 150 parts toluene under reflux for.

3 to 5 hours. a Sodium carbonate isthen added and the toluene isremoved by distillingwith I steam.' The aqueous residue containing the azo-arylide product insusp'ension therein is filtered, and the precipitateis" washedvvith water. The product isthen purified by dissolving, in dilute, 1 to2 per cent, caustic alkali solution ,filtering from unreacted amino-azobenzene, and precipitating by acidification of the alkaline solution. V Cotton yarn is padded with a slightly alkaline solution of 'the above azosarylide to p which. may be added advantageously, but not necessarily, formaldehyde and .a fixative,

such as Turkey red oil or'an aluminum salt.

The material is then dipped'in acold solution of sodium acetate or carbonate, and the dye is developed by adding a di'azo solution derived The color developed formula;

' Ewample 2 By'similar procedure as described in EX- ample 1 the para-nitro-benzene-azo-toluldldeV of 2.3-hydroxy-naphthoic acid is prepared by, 7

coupling para-nitraniline with ortho-toluidine and condensing the resultant amino-azo compound with2.3-hydroxy-naphthoic acid. The dye is developed by treatment with the diazo solution from ortho-amino-diphenyl ether.

The dyestuif has the ztormula;

O H; R v OONRGMP NOQ Ewample 3 p 7 Aniline isdiazotized and coupled 'with Bo-p 1 omov e one 1V\I=N' naphthyl-Iamin'e, and the amino-azo com-c pound is condensed with 2.3-hydroxynaphthoic acid. VThe; dye is developed by treatment with the 'di'a'zo solution from ai The coloris a deep shade, The dy'estufi has the formula The color is a bright carmine red. 7

with 2.3-hydroxy-naphthoic acid. The dye is developed by treatment with the diazo solution from 3,4-dichlor-aniline. The color is a brilliant scarlet. The dyestuflf has the formula;

Example 5 Example 6 y Meta-nitraniline is diazotized and coupled with a-naplithyl-amine, the product con-- densed with 2.3-hydroxy-naphthoic acid, and the resultant azo-arylide coupled with diazotized para-amino acetanilide. -The color is a clear bordeaux. The formula;

N=NONHCQCHa V I In addition to the foregoing representative Example 4 examples, a very large number of other dye- V V r ings have beenmadeby the same general Anll ne ,1s dlazotlzed and coupled wlth method, several of wh ch are listed in the oi naphthylamine, and the product condensed appended table. 1

' 2.3-hydroxy-naphthoic acid'arylide from i V I v I -Ooup1edwith diazotized arylamine v Color diazotized amine+arylamine V aniline aniline 2-chlor 4-nit rani1ine 0ta gered anil ne aniline dianisidiue Dark violet anil ne aniline benzene-azo-B-napl1thyl-amins Carmine aniline aniline 4-nitro-benzene-azo-2-tolu.idine Red brown 4-mtran l1ne 2-t01uidine' 4-amino-acetanllide Mulberry 4-nitran linei 2-to1uidine a-naphthylainiue Red violet 4-n1tran1l ne 2-toluidine c amino-naphthyllienyl-ether r Blue violet 4-nitranihne 2-toluidine B-nitraniline Ora ge aniline fl-naphthylamine 3, 4 diohloraniline Poneeau anlhne B-naphthylamine 2-nitro-4-phenetidin Red violet aniline fl-naphthylamine anthranilie acid Redv aniline B-naphthylamine Z-amino-diphenyl Scarlet 2.3-hydroxy-naphthoic acid arylide from Coupled with diazotized arylemine Oolor diazotized amine+arylamine 6 aniline a-naphthylamine z-amino-diphenyl other Scarlet aniline a-naphthylarnine a-naphthylamine Violet red I aniline a-naphthylamine 4, 4-diamino-diphenyl ether Ponceau aniline a-naphthylamine 4-nitraniline Orange red 4-phenet1'dine a-naphthylamine 4-amino-acetanil1de Violet red 4-phenetidine a-naphthylamine Z-amino-diphenyl Eosin 4-phenetidine a-naphthylamiue amino-azo-benzene Bordeaux 4-phenetidine a-naphthylamine phenetol-azo-a-naphthylamme Gray blue 10 3-nitraniline a-naphthylamine amino-naphthyl phenyl ether Blue violet 3-nitrani1ine a-naphthylamine 4, 4-dia1m'no-diphenyl ether Rose, 3-nitraniline a-naphthylamine I 3-nitram'line Orange 3-mtraniline a-naphthylamine 3-nitrobenzene-azo-a-naphthylamme Black While in the detailed Example 1 the cotton fibre has been specifically referred to'as the material to be dyed with the'hereindescribed new dyestuffs, other natural or synthetic textile fibres may likewise be dyed therewith, such as silk or rayon or the like. Itis immaterial as regards the novelty of my invention whether the dye is applied by developing on the fibre or prepared in substance for use as a pigment. Mordanting or other auxiliary treatments for promoting theabsorption of the dye by the fibre, or after-treatment with metallic salts, e. g. chromium, copper or aluminum salts, fo'r fixing thedyeor modifying its color tone may be optionally employed without departing from the spirit of my invention, which is intended to include not only the dyestufi's of the general type herein described, but also material dyed therewith.

In the following claims it isunderstood that the invention comprehends the coupling of the herein described azoarylides of 2.3-hydroxy-naphthoic acid equally with dia'zotized or tetrazotized arylamines, as well as the azodyestuifs derived therefrom.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed.

I therefore particularly point out and distinctly claim as my invention 1. The method of making an azo dye which comprises coupling a diazotized' aromatic amino compound with an azo-arylide of 2.3-

hydroxynaphthoic acid having the general wherein Band B represent nuclei of the benl zene or naphthalene series which may also produce an azo-arylide having the general formula wherein R and R represent nuclei of theben-- zene or naphthalene series which may also .bear substituents of the class consisting of nitro, alkyl, and alkoxy groups, and then coupling such azo-arylide with a diazotized aromatic amino compound. a

3. As a new product, an azodye having bearsubstituents of the 'class consisting of" nitro,-alkyl, and alkoxy groups, X repre-' -sentsthe residue of a diazotized aromatic.

amino compound, and n is the number of 7 amino compound. g p

4-. As a; new product, an azodye'having the general formula; 7 r

' 1y=N.-Y

diazo groups in such 'dia-zotized aromatic wherein R and R represent nuclei of the benzeneor naphthalene series which may also bear substituents of the class consisting of nitro, alkyl and alkoxy groups and wherein Y represents a residue ofa diazotized aro-, matic amino compound. I r Signed byme this20 day of April, 1929.

a .ERNEST FeR TH R;

bear substituents of theclass consisting of nitro, alkyl, and alkoxy groups. p 2. The method of making an azo dye which comprises condensing an amino-azo compound with 2.3 -hydroxynaphthoic acid to 'i'zo i 

